AbstractUnderstanding charge transports in organic films is important for both fundamental science and practical applications. Here, contributions of off-diagonal (structural) and diagonal (energetic) disorders to charge transports were clarified using molecular-based multiscale simulation. These disorders, important for understanding charge transport in organic systems, are investigated by comparing crystal and amorphous aggregates of N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine (NPD). Although NPD has been used as a hole transport material, it also exhibits comparable electron mobility experimentally. The experimental mobility and its electric field dependence in amorphous layers were reasonably reproduced by the multiscale simulation, confirming the electron transport properties of NPD. We assumed that the structural disorder would lower mobilities; however, the mobilities were found to be independent of the degree of structural disorder. Energetic disorder markedly lowered charge mobility instead. Charge migration in crystals was dominated by maximum electronic coupling pairs, whereas small electronic coupling pairs significantly contributed to charge transport in amorphous aggregate.